Silver halide emulsions sensitized with methine dyes containing a cyclopentanone nucleus

ABSTRACT

NOVEL METHINE DYES CONTAINING A CYCLOPENTANONE NUCLEUS IN THE METHINE CHAIN ARE PREPARED BY THE ACID HYDROLYSIS OF CYANINE ENAMINE DERIVATIVES. THESE METHINE DYES ARE SPECTRAL SENSITIZERS FOR PHOTOGRAPHIC SILVER HALIDE EMULSIONS. A NUMBER OF THE NEW DYES EXTEND TO SENSITIVITY OF PHOTOGRAPHIC SILVER HALIDE EMULSIONS INTO THE RED AND NEAR INFRA-RED REGIONS OF THE SPECTRUM.

United States Patent once 3,672,906 Patented June 27, 1972 ,67 ,90SILVER HALIDE EMULSIONS SENSITIZED WITH METHINE DYES CONTAINING A CYCLO-PENTANONE NUCLEUS Leslie G. S. Brooker, Rochester, and Arthur Fumia,Jr.,

Hilton, N.Y.,-assignors to Eastman Kodak Company, Rochester, N. a

No Drawing. Continuation-impart of application Ser. No. 656,647, July28, 1967. This application Mar. ,25, 1970,

Ser. No. 22,707 Int.'Cl. G03c 1/08 Us. or. 96-142 .7 s Claims ABSTRACTOF THE DISCLOSURE Novel methine dyes containing a cyclopentanone nu-'cleus in the methine chain are prepared by the acid hydrolysis ofcyanine enamine derivatives. These methine dyes are spectral sensitizersfor photographic silver halide emulsions. A number of the new dyesextend the sensitivity of photographic silver halide emulsions into the2 red and near infra-red regions of the s'pectrum.

spectrally sensitized with a methine dye comprising anitrogen-containing heterocyclic nucleus having from 5 to 6 atoms in theheterocyclic ring, said nucleus being of the type used in cyanine dyes,said heterocyclic nucleus being joined by a dimethine linkage to the2-carbon atom of a cyclopentanone nucleus.

Especially useful dyes which sensitize photographic silver halideemulsions to infra-red radiation are those which comprise first andsecond nitrogen-containing heterocyclic nuclei containing from 5 to 6atoms in the heterocyclic ring, said nuclei being of the type 'used incyanine dyes, said first nucleus being joined by a di methine linkage tothe Z-carbon atom of a cyclopentanone ring, and said second nucleusbeing joined by a dimethine linkage to the S-carbon atom of saidcyclopentanone nucleus.

The preferred cyanine dyes of the invention are rep- I resented by thefollowing general formulas:

This application is a continuation-impart of our copending U.S.application Ser. No. 656,647- filed July 28, 40

1967, now abandoned.

This invention relates to novel photographic materials, and moreparticularly to photographic silver halide emulsions spectrallysensitized with methine dyes.

We have now found that certain methine dyes are" excellent spectralsensitizers for bothblack and white and color photographic silver halidematerials. 'A'-number of these new dyes extend the sensitivity ofphoto-' graphic silver halide emulsions into the red and near infra-redregions of the spectrum. 1 1

It is one object of this invention to provide light sensitive silverhalide spectrally sensitized with methine dyes. Another object of thisinvention is to provide'photographic silver halide emulsions containingcertain methine dyes. i

Other objects of this invention will become apparent from aconsideration of the general'description and examples, and the appendedclaims. 1

In accordance with one embodiment of this invention, light sensitivephotographic silver halide emulsions are H. om

wherein mtand n 'each represents a positive integer'of from to 2, and Rand R each represents an alkyl group, preferably a lower alkylcontaining from 1. to 4 carbon atoms, e.g., methyl, ethyl, propyl,isopropyl,

- group, e.g., phenyl, naphthyl, tolyl, chlorophenyl, sulfophenyl,carboxyphenyl, etc.; and, Z and Z each represents the nonmetallic atomsrequired to complete a 5- to 6-me1'nbered heterocyclic nucleus such as athiazole nucleus (e.g., thiazole, methylthiazole, 4-phenylthiazole, 5-

EXAMPLE 1 2,5 -bis[ (3-ethyl-2- benzothiazolinylidene) ethylidene]cyclopentanone o I (i v C=CHQH=C/' \C,-OZHCH=C H2C--CH2 3,3-diethy l10,12 ethylene ll (l-pyrrolidinyDthiatri carbo'cyanine iodide (6.4 g), 1mol.), water (25 ml. and 36% hydrochloric acid (2 m1.)"are mixed andheated under reflux with stirring. The mixture was diluted several timeswith additional acid and water, with refluxing, continued until theabsorption of the starting material had disappeared. After chilling, thesolid is collected on a funnel, washed withacetone and dried. After tworef crystallizations from pyridine/methanol, the yield of purified dyeis 2.1 g. (46%) MP. 246-247 C. decomposes.

In place of the 3,3'-diethyl-10,12-ethylene-ll-(l-pyrrolidinyl)thiacarbocyanine iodide in the above example, there can be substitutedan equivalent amount of, for example, 331dit-hyl-IOJZ-ethylene-ll-(l-pyrrolidinyl) oxatricarbocyanine salt suchas the chloride, bromide, iodide, etc. or a3,3'-diethyl-10,12-ethylene-ll-(l-pyrrolidinyl) selenotricarbocyaninesalt or "a 3,3'diethyl-10,12- ethylenell-(1-pyrrolidinyl)thiazolotricarbocyanine salt, and the' likeyto givethe corresponding cyanine dyes of the invention having generally similarspectral sensitizing properties when incorporated in photographic silverhalide emulsions.

' EXAMPLE 2 I 2,5-bis l-ethylnaphtho[11,2-d]thiazolin-2 ylidene) 7 1ethylidene]cyclopentanone' 3,3-diethyl 10,12 ethylene-11(1-pyrrolidinyl)-'4,5,4',5- dibenzothiatricarbocyaninep-toluenesulfonate (3.9 g., 1 mol.), water (75 ml.) ethanol (200 ml.)and 36% hydro'chloric acid (5 ml.) 'are heated under reflux withstir:ring. The mixture is diluted several times with'additional for example,3-ethyl-2-{2-,[2-(l-pyrrolidinyl)cyclopentyl] EXAMPLE 3-2',5-bis[-(1,3;3 trimethyl-2 indolinylidene)-'ethylidene]cyclopentanone EXAMPLE 4 .2-[(3ethyl-Z-benzothiazolinylidene)ethylidene] cyclopentanone N Hz 3ethyl-2% 2-[2-(l-pyrrolidinyl)cyclopentenyl] vinyl benzothi-azoliumiodide (6.0g. 1 .mol.) is treated with water and 36% hydrochloric acidin the manner as Example 2. After two recrystallization from .l yridine/methanol, the yield of purified dye is 1.1 g. (31%), MP.

230-231 C. dec.

lnplace of the 3-ethyl-2-{2-[Z-U-pyrrolidinybcyclopentyl]v1nyl}benzothrazolium iodide inthe above exam ple, there can be substituted an equivalent ainountof:

viny1}benzoxazolium salt such as the bromide, chloride, iodide,'etc.,[or the corresponding selenazolium salts, or the cor'respondingthiazoliurn salts, and theflike,to give the corresponding cyanine dyesof the invention thatlike- Wise extend the sensitivity of photographicsilver halide emulsion, at the concentrations indicated in the followingTable 1. The dyes are exposed to a minimum amount of sensitized silverhalide emulsions is employed. After digestion at, 50-52 C. for about ,10minutes, the emulsions acid and water with refluxing continued until.the'absorp tion of the startnig material has disappeared. Afterchilling, the solid is' collected on "a funnel, washed with metha' noland dried. Atfter two recrystallizations from pyridine/ methanol,theyield of purified dye is 0.9 g. (32% -MLP. 275-276 C. dec. v, V p In'place of thel3,3'-diethyl-l0,12 ethylene- (l-pyrrol idinyl) 4,5,4',5'dibenzothiacarbocyanine p-toluenesulfonate in ,the above example therecan be substituted an equivalent amount of, for example,3,3-diethyll0,l2-' ethylene-(l-pyrrolidinyl) 4,5,4',5'dibenzoxatricarbocyaninesaltsuch as the chloride, bromide iodide, etc,to give thecorres p'ondin'g cyanine dye of'the invention hav inggenerally similar spectral'sensit-izing properties for photographicsilver halide emulsions.

are coated at a coverage of 459 mg. of silver and 1040 mg. of gelatinper square foot on a cellulose'acetate film support. A sample of eachcoating is exposed on an Eastman? 13 sensitometer and to a wedgespectrograph, proc essed for 5 minutes in Kodak DK-SO developer(Handbook of Chemistry and Physics, 30th edition, 1947, Chemical RubberPublishing Co., Cleveland, Ohio, page 2558) having the followingcomposition:

G. N-methyl-p-aminophenol sulfate 2.5 Sodium sulfite (desiccated) 30.0Hydroquinone v E 2.5 Sodium metaborate 10.0

Potassium bromide -2-.. 0.5

Water to make 1.0 liter.

and then fixed in a conventional sodium thiosulfate fixing bath, washedand dried. The sensitizing values obtained are shown in the followingTable l. p

I TABLE 1 Dye and i f Dye of eoneentra- Sensitization (m Examtion .I V vple No. mole silver Emulsion type Range 7 Maximum 0. 103 Silverchlorobromide 760 to 810. 790

0.13 do-.- 500 to 705.

1 No definite maximum.

The following examples illustrate the preparation of the intermediatedye compounds employed in the procedures of above Examples 1 to 4 toprepare the cyanine dyes of the invention. As indicated previously,additional details for the preparation of these and related dyeintermediates can be had by reference to the aforementionedR. A.Jetfreys copending application, Ser. No. 518,010, filed Jan. 3, 1966.

EXAMPLE 3,3-diethyl-10,12-ethylene-1l-(l-pyrrolidinyl)thiatricarbocyanine iodide N-cyclopentenylpyrrolidine (0.7 gram),2-[2-ac'etanilidovinyl] 3 ethylbenzothiaziolium iodide (4.5]grams) andsodium acetate (0.8 gram) in acetic anhydride (25 ml.) are refluxedtogether for hour, and the resulting blue solution is chilled toprecipitate the dyeproduct formed. The, dye product isrfiltered off,washed with ethanoLandwater; and recrystallized from methanol "as mossgreen-needles, M.P. above345 C., in 1 gram (31%) yield; 4 EXAMPLE-6 Y l3,3'-- diethyl 10,1 2- ethylene -11 (1 pyrrolidin'yl)- 2 (2-anilinovinyl) l ethyl-naphtho[1,2- d] thiaz'oli um p-toluenesulfonate'(21 g;, 2 mols. +5%')', N-cyc1opentenylpyrrolidine 2.7 g.', '1" mol'.),-triethylenediainine (7.4 3., 2 mols; and acetic anhydride (317 ml., 2rhols.) are dissolved in N,N-dimethylacetanjide (40 m1.) and heated on asteam bath, with stirringp-forone-half hour. After chilling, the crudeproduct is collected ona filter,v washed with methanol and dried.Attertwo re.- crystallizations from methanol, the yield oftpu'rified dyeis 6.1 g. (39%), M.P. 253-254 C. dec.

tdibenzothiatricarbocyanine p-toluenesul- .e 50

v of those prepared withflh'ydrophilic colloids EXAMPLE 7 10,12ethylene-1,l,3,3,3T,3'hexamethyl-1.1-( l-pyrrolidinyDindOtricarbQcyanineiodide N-cyclopentenylpyrrolidine1267; grams) and 2-[2-acetanilidovinyl] 3 ethylbenzothiazolium iodide (9 grams) in ethanol (25ml.) are shaken togetherat room temperature for hour. 1 Thev dye productformed is filtered otf and recrystallized from ethanol to remove magentaand blue impurities. The orange dye is obtained as maroon leaflets, M.P.297-299 C. with decomp.

(darkens at 290 c. in 2.1; grams (23%) yield. A

v N-cyclopentenylpyrrolidine I mo-cn. E 1 5, 7 H1 H: I I y N 5 Hr0 0,Hp

v H *-CHz This compound isprepared in the mariner described 1.5, byGIStark, et aha]. Am. Chem.jSoo., 85,' 216G963);

For the. preparation of photographic emulsions," this new dyesof theinventionare advantageously incorporated in the finished silver halideemulsion and shouldfdjf course be uniformly distributed'throughout theemulsion;

. Themethod of incorporating dyes in emulsions are "relai tively simpleand well known to those skilled in the art of emulsion making. Forexample, itis convenient to addthe dyes from solutions in appropriatesolvents; in. which the,solvent selected should have "no deleter ioiiseffect on the ultimate light-sensitive materials; Methanol,

isopropanolal yridine etc. alone orin eombinat'iorrhave provensatisfactory as solvents for the majority of the new dyes of theinvention. The type of silver halide emu1 sions that are sensitized withthe new dyesinclu'de any atl e known to be satisfactory for dispersinglight-sensitive 9 silver halides, for examples, emulsions prepared withhydrophilic colloids, such as natural materials, e.g., gelatin, albumin,agar-agar, gum arabic, alginicacid, etc., and synthetic hydrophilicresins, e.g., polyvinyl alcohol, poly- 10 chloroplatinate (Trivelli etal. US. Pat. 2,566,245, issued Aug. 28, 1951), ammonium chloroplatinite(Trivelli et al. US. Pat. 2,566,263, issued Aug. 28, 1951),benzotriazole, nitrobenzimidazole, S-nitroi'ndazole, benzidine,mercapvinyl pyrrolidone, cellulose ethers, partially hydrolyzed tans,etc. (see MeesTh e.Theory of the Photographic cellulose acetate, etc.Process, MacMillian Pub., 1942, page 460), or mixtures The concentrationof'the new dyes in' the emulsions can thereof; hardeners, such asformaldehyde (Miller US. Pat. be widely varied, i.e., generally fromabout 5 to about 1,763,533, issued June 10, 1930), chrome alum (1,763,-100 mg. per liter of flowable emulsion-The specific con- 533), glyoxal(Brunken US. Pat. 1,870,354, issued Aug. centration will vary accordingto the type of light-sensitive 9, 1932), dibromacrolein (Block et al.British Pat. 406,- material in the emulsion and according to the effectsde- 750, accepted Mar. 8, 1934), etc.; color couplers, such as sired.The most advantageousdye concentration for any those described inSalminen et al. US. Pat. 2,423,730, given emulsion can be readilydetermined by making the issued July 7, 1947, Spence and Carroll US.Pat. 2,640,- tests and observations customarily used inthe art of 776,issued June 2, 1953, etc.; or mixture of such addenda. emulsion making.The emulsions are coated to advantage Dispersing agents for colorcouplers, such as those set on any of the support materials commonlyused for phoforth in Jelley et al. US. Pat. 2,322,027, issued June 15,tographic elements, for example, paper, glass, cellulose de- 1943, andMannes et al. US. Pat. 2,304,940, issued Dec. rivatives, such ascellulose acetate, cellulose acetate-pro- 15, 1942, can also be employedin the above-described pionate, cellulose nitrate, etc., syntheticresins, such as emulsions. poly styrene, polyethylene terephthalate andother poly- The invention has been described in detail withparticuesters, polyamides, such as nylon, and the like. lar reference topreferred embodiments thereof but it will To prepare a gelatino-silverhalideemulsion desens ibe understood that variations and modificationscan be tized with one of the new dyes, thefollowing procedure iseffected within the spirit and scope of the invention as desatisfactory:A quantity of dye is dissolved in a suitable scribed hereinabove and asdefined in the appended solvent, and a volume of this solutioncontaining the declaims. r sired amount of dye is slowly added withintimate mix- We claim; ing to about 1,000 cc. of light-sensitivegelatino-silver ha- 1. A light-sensitive photographic silver halideemulsion lide emulsion. With most of the new dyes, from about spectrallysensitized with a methine dye comprising a 10 to 20 mg, of dye per literof emulsion suffices to proheterocyclic nucleus selected from the groupconsisting duce the desired sensitizing effect with the ordinary gelaofa thiazole nucleus, abenzothiazole nucleus, a naphtino-silver' halidesincluding silver chloride, bromide, thothia'zole nucleus, athianaphtheno-7',6',4,S-thiazole nubromoiodide, chlorobromide,chlorobromoiodide, etc., cleus, an oxazole nucleus, a benzoxazolenucleus, a naphthemulsions. With fine-grain emulsions which include mostoxazole nucleus, a selenazole nucleus, a benzoselenazole of the ordinaryemployed gelatino-silver chloride emulnucleus, a naphthoselenazolenucleus, a thiazoline nusions, somewhat larger concentrations of dye maybe cleus, a Z-quinoline nucleus, a 4-quinoline nucleus, a 1- necessaryto secure optimum sensitizing effect. While the isoquinoline nucleus, a3-isoqinoline nucleus, a 3,3-dialkylpreceding has dealt with emulsionscomprising gelatin, it indolenine nucleus, 21 pyridine nucleus, animidazole nu-' will be understood that these remarks apply generally tocleus', a benzimidazole nucleus and a naphthimidazole n11- any emulsionsin which a part or all of the gelatin is subcleus; said heterocyclicnucleus being joined by a distituted by another suitable hydrophiliccolloid such as 40 methine linkage to the Z-carbon atom of acyclopentanone' those previously mentioned. nucleus. 8 The abovestatements are only illustrative and are'not 2. A light-sensitivephotographic silver halide emulsion to be understood as limiting theinvention in any sense,-as spectrally sensitized with a cyanine dyecomprising first it will be apparent that the new dyes can beincorporated and second nitogen-containing heterocyclic nuclei sebyother methods in many of the emulsions customarily lected r m the groupconsisting of a thiazole nucleus, a used in the art. For instance, in aless preferred method, benzothiazole nucleus, an naphthethiazolenucleus, a thiathe dyes can be incorporated by bathing a plate orfilm.naphtheno-7',6,4,5-thiazole nucleus, an .oxazole-nucleus, bearing anemulsion, in a solution of the dye. a benzoxazole nucleus, anaphthoxazole nucleus, a selen- Ph'otogfaphic Silver halide e lsions,Such as those azole nucleus, at benzoselenazole nucleus, anapththoselenlisted abOVe, containing the Sensitilillg y 0f t azolenucleus, a thiazoline nucleus, a 2-quinoline nucleus, tion can alsocontam K addenda as chqmwal 9 a 4-quinoline nucleus, a l-isoquinolinenucleus, a 3-isotizers, e.g., sulfur sens1tizers (e.g., allylthlocarbamide, quinoline nucleus, a 33 dialkyfindolenine nucleus, athiourea, allyhsothiocyanate, cystme, etc.), var1ous gold idine nucleus,an imidazole nucleus, a benzimidazole cpmpounds pota.ssmm chloroaurateaunc i cleus and a naphthimidazole nucleus; said first heteroetc) (seeBaldslefen 2540385 i 55 cyclic nucleus being joined by a dimethinelinkage to the Feb. 6, 1951; Damschroder US. Pat. 2,597,856, issued b tf I t l d May 27, 1952 and Yutzy et al. US. Pat. 2,597,915, issued a a 8i t i May 27, 1952), various palladium compounds such as 7 0ndheterocycllc nucleus belng omed by a dlmethlnehnkpalladium chloride(Baldsiefen US. Pat. 2,540,086, issued age to f PP atom of Sald cyclopentan one q Feb. 6, 1951), potassium chloropalladate (Stauffer' etal.. A h senltlve'p hotographl sllver hahd? emulsion US. Pat. 2,598,079,issued May 27, 1952 etc., or mixsp y sensitlzed Wlth a methme dye havmsone of tures of such sensitizers; antifoggants, such as ammonium tfollowing formulas:

0 t I, -Z R-N(CH=CH)n -i*C=CHCH=(IJ CIJHQ H2C'-UH2 and 0 ll --z-. 0Z1....- 1 RMN (-CH=CH) n -C=CH-CH=C C=CHCH=C CH GH)m-I' N' RI ,l 11 a.wherein m and n each represents a positive" integer of from 1 to 2; Rand R each represents a member selected from the group consisting of analkyl group, an allyl group, and an aryl group; and, Z and Z eachrepresents the non-metallic atoms necessary to complete a heterocy- 5and'an y p; and Z and 1 h P PFI #1 9 Clic 1111016118 Selected 1116 groupconsisting of a thiaf metallic atoms necessary to complete aheterocyclic nu zole nucleus, a benzothiazole nucleus, a naphthothiazoleimc e s, a thianaphtheno 7,I6,I45 thiazole nu an celus selected, frornthe group .conslstmg of a thlazole oxazole nucleus, a benzoxazolenucleus, a naphthoxazole I I s a benzothlazole naphthothlazole Inucleus, at selenazole nucleus, at benzoselenazole nucleus, 10 e eu S, athiauaphthenoJ';Q',4,-th1azo1enucleus, an oxa- Pl i I 1 1 4 l inthlilolmfi i l f' far zole nucleus, henzokazole nucleus, a, naphthoxazole qumo e nuc eus, a -qumo e nuc eus, a -1s oqu1no me I I p nucleus, a3-isoquinoline nucleus, at 3,3-dialkylindolenine P a SelenazolenIucleusf a f f p nucleus nucleus, a pyridine nucleus, an imidazolenucleus, at benz-J. I E 'naphtmselenalole 131919115, flnaolflw111191595, 3 i-midazole nucleus and a naphthimidazole nucleus, 7 l5quinoline nucleus, at 4-quinoline nucleus, a lisoquino'line A light RRhotographl c silver l Fmulslon nucleus, a 3-isoquinoline nucleus, a3,3-dialkylindolenine spectrally sensitized with a methlne dye havngthev foll lowing formula: H h I I nucleus, a pyridlne nuc eus, an lmida-zole nucleus,'abenzo I II 1. I imidazole nucleus andanaphthimidazole'nucleus, I

ll I 6. A light 'sensitive'Iphotographic silverfhalide emulsion CH=CH)III (-J=C CH: I spectrally sensitized with a cyanine. dye selected from vthe 'group consistingof- 1 i Ha .Ha v I I ."-f wherein n represents apositive integer of from 1 $12;2,5-bis[(3-ethyl-2-benuothiazolinylidene)eth fi j R represents a memberselected from the group consisting cyclopentanong, t I II I I of a alkylg p allyl g p and an al'yl 8MP;2,5-bis[(1-ethylnaphtho[.1,2-d]thiazolin-2-ylidene) 1 Z represents thenon-metallic atoms necessary to complete I I ,I I I a heterocyclicnucleus selected from the group consisting I ethylldenelcxclopemanons, IY of a thiaz ole nucleus, at benzothiazole nucleus, a naph-2,5-bis[(1,3,3-trimethyl-2-indolinylidene)ethylidene] thothiazolenucleus, a thianaphtheno-7',6',4,5-thiazole I cyclopemanone and Inucleus, an oxazole nucleus, a benzoxazole nucleus, at 2 3 h 12b dnaphthoxazole nucleus, a selenazole nucleus, an benz o- I l T enzo m Y Py g II selenazole nucleus, a naphthoselenazole nucleus, a thiazpen anonI I oline nucleus, a Z-quinoline nucleus, a 4quin0line nucleus, I K amsoquinoline nucleus, a 3.,isoquino1ine nucleus, 3 7. A l ght sensitivephotographic silver halide emulsion dialkylindolenin e nucleus, 9.pyridine nucleus, an imidazole spectrally sensitized with2,5-bis[(3-ethyl-2 henzothiaz a benzimidazole nucleus and anaphthlmidazole olinylidem)Iethylidene]cyclopentanoneI I I I I I 5. Alight sensitive photographic silver halide emulsion 40 A'hght i l fl ifisilver fi m spectrally, sensitized with a dye having the following t lSensltlzed h fifin ld formula:- I Y 7 i llinylidene)ethylidene]cyclopentanone. I l

" k v l 0 a v r A r a Y R1 l(-C =cH)l.-1- J=0u-cn=o c=cH-cn=(-c1r=cHm-1-$I-m 5 7 References .Cited I UNITED STATES PATENTS I 2,860,98411/1958 Jones 96-140 3,140,182 ,7/1964 Haseltine et a1. 96--l413,148,065 9/1964 Craig et a1. 96-140 FOREIGN PA TENTS 595,785 12/1947Great Britain.

l 12 A, wherein m and n represents a positive integer of from t to 2; Rand R each represents am'einber selected frorriI the group consisting ofan alkyl group, an allyl group,

J. TRAVIS BROWN, Primary Examiner us. 01. X.R.

